Amino terminated phosphonamide oligomers and flame retardant compositions therefrom

ABSTRACT

The invention relates to the use of amino terminated phosphonamides and their oligomers, as flame retardant additives for a variety of polymers to impart flame retardancy while maintaining or improving processing characteristics and other important properties.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. Provisional Application No.61/412,612 entitled “Amino Terminated Phosphonamide Oligomers and FlameRetardant Compositions Therefrom” filed Nov. 11, 2010, which is hereinincorporated by reference in its entirety.

GOVERNMENT RIGHTS

This invention was developed with Government support under Contract No.FA8650-07-C-5907 awarded by the Department of the Air Force. TheGovernment has certain rights in the invention.

PARTIES TO A JOINT RESEARCH AGREEMENT

Not applicable.

INCORPORATION BY REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC

Not applicable.

BACKGROUND

The phosphorus content of polymer compositions is important to achievingflame retardancy. High molecular weight polyphosphonamides often havepoor solubility or miscibility in the host polymer, and due to theirhigh melt viscosity, significantly detract from the melt processabilityof the host resin. When added to thermosetting polymers, a reduction inglass transition temperature (Tg), heat distortion temperature (HDT),and modulus often results. Additionally, adding high molecular weightpolyphosphonamides to other polymers leads to a lower phosphorus contentcompared to using oligomers.

Amino terminated phosphonamide oligomers can react with a variety ofmonomers and oligomeric species to form copolymers. For example, theycan be co-reacted with epoxy formulations to produce a flame retardantpolymer in which the phosphonamide oligomer is chemically incorporatedinto the matrix via covalent bond formation. Likewise, the aminoterminated phosphonamide oligomers can be used as reactants to formcopolyamides, copolyureas, copolyimides and any other copolymers thatcan react with an amine functional group. Therefore, there is a need forphosphonamides prepared by any synthetic route that have reactive aminoend groups at sufficient concentration to participate in bond formingreactions with other monomers or reactive species to form copolymers.

SUMMARY OF THE INVENTION

Embodiments described herein include a composition comprising an aminoterminated phosphonamide of general Formula I:

where R is a C₁ to C₂₀ alkyl or, optionally substituted, aryl group, Xis an aromatic or aliphatic group, Z is:

andn is an integer of from 1 to about 20. In some embodiments, n can be aninteger of from 1 to about 10. In other embodiments, theamino-terminated phosphonamide may include at least about 50% amineend-groups based on the total number of end groups. In certainembodiments, R may be methyl, and in some embodiments, each —NH—X—NH—can be derived from a diamine, a triamine, or a polyamine.

Other embodiment are directed to compositions including an aminoterminated phosphonamide of general Formula II:

where each of R¹⁻⁵ is individually a C₁ to C₂₀ alkyl or, optionallysubstituted, aryl group, each of X¹⁻⁴ is individually, an aromatic,cycloalkyl, or aliphatic group, n and m are each individually an integerof from 0 to about 20 and each Z is, independently:

In some embodiments, each m and n are each individually integers from 0to about 10. In other embodiments, the amino-terminated phosphonamideincludes at least about 50% amine end-groups based on the total numberof end groups. In particular embodiments, each of R⁻⁵ can be methyl, andin other embodiments, each of —NH—X¹⁻⁴—NH— can independently derivedfrom a diamine, a triamine, or a polyamine.

Further are directed to compositions that include the amino terminatedphosphonamide of the invention including those of Formulae I and II andone or more polycarbonates, epoxy derived polymers, polyepoxies,benzoxazines, polyacrylates, polyacrylonitriles, polyesters,poly(ethylene terephthalate)s, poly(trimethylene terephthalate) andpoly(butylene terephthalate)s, polystyrenes, polyureas, polyurethanes,polyphosphonates, poly(acrylonitrile butadiene styrene)s, polyimides,polyarylates, poly(arylene ether)s, polyethylenes, polypropylenes,polyphenylene sulfides, poly(vinyl ester)s, polyvinyl chlorides,bismaleimide polymers, polyanhydrides, liquid crystalline polymers,cellulose polymers, and combinations thereof, and in some embodiments,these compositions may further include one or more fillers, fibers,surfactants, organic binders, polymeric binders, crosslinking agents,coupling agents, additional flame retardants, anti-dripping agents,anti-static agents, catalysts, colorants, inks, dyes, antioxidants,stabilizers, or combinations thereof.

Still further embodiments are directed to methods for preparing theoligomeric amino terminated phosphonamides of the invention includingthose of general Formulae I and II, and methods for preparingcompositions including the oligomeric amino terminated phosphonamidesand another thermoplastic or thermoset resin. Additional embodimentsincluding articles of manufacture and various coatings and moldingscreated from the oligoemeric amino terminated phosphonamides of theinvention and compositions including these oligomeric amino terminatedphosphonamides.

DESCRIPTION OF DRAWINGS

Not applicable.

DETAILED DESCRIPTION

Before the present compositions and methods are described, it is to beunderstood that this invention is not limited to the particularprocesses, compositions, or methodologies described, as these may vary.It is also to be understood that the terminology used in the descriptionis for the purpose of describing the particular versions or embodimentsonly, and is not intended to limit the scope of the present invention,which will be limited only by the appended claims. Unless definedotherwise, all technical and scientific terms used herein have the samemeaning as commonly understood by one of ordinary skill in the art.Although any methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of embodimentsof the present invention, the preferred methods, devices, and materialsare now described. All publications mentioned herein are incorporated byreference in their entirety. Nothing herein is to be construed as anadmission that the invention is not entitled to antedate such disclosureby virtue of prior invention.

It must also be noted that, as used herein and in the appended claims,the singular forms “a”, “an”, and “the” include plural reference unlessthe context clearly dictates otherwise. Thus, for example, reference to“a combustion chamber” is a reference to “one or more combustionchambers” and equivalents thereof known to those skilled in the art, andso forth.

As used herein, the term “about” means plus or minus 10% of thenumerical value of the number with which it is being used. Therefore,about 50% means in the range of 45%-55%.

The terms “flame retardant,” “flame resistant,” “fire resistant,” or“fire resistance,” as used herein, means that the composition exhibits alimiting oxygen index (LOI) of at least 27. “Flame retardant,” “flameresistant,” “fire resistant,” or “fire resistance,” may also refer tothe flame reference standard ASTM D6413-99 for textile compositions,flame persistent test NF P 92-504, and similar standards for flameresistant fibers and textiles. Fire resistance may also be tested bymeasuring the after-burning time in accordance with the UL test (Subject94). In this test, the tested materials are given classifications ofUL-94 V-0, UL-94 V-1 and UL-94 V-2 on the basis of the results obtainedwith the ten test specimens. Briefly, the criteria for each of theseUL-94-V-classifications are as follows:

UL-94 V-0 the average burning and/or glowing time after removal of theignition flame should not exceed 5 seconds and none of the testspecimens should release and drips which ignite absorbent cotton wool.

UL-94 V-1: the average burning and/or glowing time after removal of theignition flame should not exceed 25 seconds and none of the testspecimens should release any drips which ignite absorbent cotton wool.

UL-94 V-2: the average burning and/or glowing time after removal of theignition flame should not exceed 25 seconds and the test specimensrelease flaming particles, which ignite absorbent cotton wool.

Fire resistance may also be tested by measuring after-burning time.These test methods provide a laboratory test procedure for measuring andcomparing the surface flammability of materials when exposed to aprescribed level of radiant heat energy to measure the surfaceflammability of materials when exposed to fire. The test is conductedusing small specimens that are representative, to the extent possible,of the material or assembly being evaluated. The rate at which flamestravel along surfaces depends upon the physical and thermal propertiesof the material, product or assembly under test, the specimen mountingmethod and orientation, the type and level of fire or heat exposure, theavailability of air, and properties of the surrounding enclosure. Ifdifferent test conditions are substituted or the end-use conditions arechanged, it may not always be possible by or from this test to predictchanges in the fire-test-response characteristics measured. Therefore,the results are valid only for the fire test exposure conditionsdescribed in this procedure. The state-of-the-art approach to renderingpolymers flame retardant is to use additives such as brominatedcompounds or compounds containing aluminum and/or phosphorus. Use ofthese additives can have a deleterious effect on the processingcharacteristics and/or the mechanical performance of products producedfrom them. In addition, some of these compounds are toxic, and can leachinto the environment over time making their use less desirable. In somecountries certain brominated additives and aluminum and/or phosphoruscontaining additives are being phased-out of use because ofenvironmental concerns.

Embodiments of the invention are generally directed to amino-terminatedphosphonamides, and in some embodiments oligomeric amino terminatedphosphonamides. Other embodiments are directed to methods for producingamino terminated phosphonamides. Further embodiments are directed tomethods for using amino terminated phosphonamides in thermoset resins,and certain embodiments are directed to thermoplastics having aminoterminated phosphonamides and oligomeric amino terminated phosphonamidesincorporated into the polymer matrix. Still further embodiments aredirected to articles of manufacture that include these thermoplasticshaving amino terminated phosphonamides and oligomeric amino terminatedphosphonamides incorporated into the polymer matrix.

Embodiments are not limited to particular phosphonamides. Various knownphosphonamides can be reformulated to include amino termini and areencompassed by the invention. In particular embodiments, the aminoterminated phosphonamides of the invention may have the structure ofgeneral Formula I:

where R is a C₁ to C₂₀ alkyl or, optionally substituted aryl group, X isan aromatic, cycloalkylene, or aliphatic group, n is an integer of from1 to about 20, and Z is:

In other embodiments, the predominately amino terminated phosphonamideoligomers may include compounds of Formula II:

where R¹⁻⁵ are each individually a C₁ to C₂₀ alkyl or, optionallysubstituted, aryl group, X¹⁻⁴ are each individually, an aromatic,cycloalkylene, or aliphatic group, n and m are an integer of from 0 toabout 20, and each Z is, independently:

In some embodiments, m and n may each independently be from about 0 toabout 10. In other embodiments, m may be an integer of from 0 to about4, such that the branching, or potential branching, and n may be anyinteger from 1 to about 10.

In particular embodiments, each —NH—X—NH— provided in Formulae I and II,including the amine containing moieties including X¹⁻⁴, may be derivedfrom an amine containing monomer including all known diamine, triamine,or polyamine containing monomer. In certain embodiments, each —NH—X—NH—may be derived from the same amine containing monomer, and in otherembodiments, each —NH—X—NH— may be derived from two or more differentamine containing monomers. Examplary amine containing monomers includealkanediamines, alkanetriamines, arylamines, cycloalkylamines, or anycombinations thereof, and in various embodiments, the alkanediamines,alkanetriamines, arylamines, cycloalkylamines may have from about 6 toabout 12 or about 20 carbon atoms. In particular embodiments, thealkanediamines, alkanetriamines, arylamines, cycloalkylamines may havefrom about 6 to about 8 carbon atoms. More specific non-limitingexamples of suitable diamines, triamines, and polyamines includem-xylylenediamine, di(4-aminophenyl)methane,di(4-aminocyclohexyl)methane, 2,2-di(4-aminophenyl)propane,1,4-diaminobutane, 1,3-bis-(aminomethyl)-cyclohexane,1,4-bis(aminomethyl)-cyclohexane,2,5-bis(aminomethyl)-bicyclo-[2,2,1]heptane and/or2,6-bis-(aminomethyl)-bicyclo[2,2,1]heptane,bis-(4-aminocyclohexyl)-derivative of an alkane having from 1 to 6carbon atoms, and p-xylylene-diamine 2,2-di(4-aminocyclohexyl)propane,and triamine derivatives of these diamines, any mixtures, orcombinations thereof. In certain embodiments, —NH—X—NH— may be derivedfrom polyether amine or Jaffamine, which are described herein below.

The weight average molecular weight (Mw) of these predominately aminoterminated phosphonamide oligomers can vary based on the number ofmonomers incorporated into the polymer chain and can be form about 200g/mole to about 10,000 g/mole or about 500 g/mole to about 7,500 g/molein embodiments (all expressed against polystyrene (PS) standards). Theterm “predominately” as used herein is meant to infer that at least 50%of the available end groups include an amine group, and in someembodiments, predominately may refer to phosphonamides having from about50% to about 100%, about 60% to about 90%, about 60% to about 80%, orany range between these exemplary ranges of amine end groups based onthe total number of available end groups.

The predominately amino terminated phosphonamide oligomers of suchembodiments may be prepared by combining an amine containing monomer anda phosphonate containing monomer and heating this mixture under vacuum.In some embodiments, the reaction mixture may further include apolymerization catalyst such as, for example, magnesium chloride. Ingeneral, the vacuum may be sufficient to remove volatile components,such as phenol, produced as the phosphonamide oligomer is made. In someembodiments, the vacuum may be applied in a step wise manner, in whichthe vacuum is increased and the pressure of the reaction is reduced oneor more times, during the polymerization process, and in otherembodiments, the pressure may be gradually reduced throughout thepolymerization. In still other embodiments, the vacuum may be increasedand the pressure reduced both step wise and gradually in the samepolymerization method. For example, in some embodiments, the vacuum maybe applied to produce an initial pressure of from about 250 mmHg toabout 50 mmHg and the pressure may be reduced gradually, in a step wisemanner, or both to from about 10 mmHg to about 5 mmHg. In otherexemplary embodiments, the initial pressure may be from about 250 mmHgto about 150 mmHg, and this pressure may be reduced to from about 40mmHg to about 80 mmHg and then reduced again to about 20 mmHg to about 5mmHg to produce a method with 3 vacuum steps. Other methods may includemore than 3 steps, and still other methods may include less than 3steps, for example, pressure may be gradually reduced throughoutpolymerization from about 250 mmHg or 150 mmHg to about 10 mmHg or about5 mmHg.

The temperature of the reaction may be maintained at any temperature atwhich polymerization may occur. For example, in some embodiments, thereaction temperature may be from about 175° C. to about 300° C., and inother embodiments, the reaction temperature may be from about 200° C. toabout 250° C. or 275° C. In some embodiments, a constant reactiontemperature may be maintained throughout the polymerization, and inother embodiments, the reaction temperature may change at various timesthroughout the polymerization reaction. In particular embodiments, thereaction temperature may be increased at steps as the pressure isdecreased. For example, in the context of the exemplary embodimentsabove, the initial reaction temperature may be about 175° C. to about220° C. when the pressure is from about 250 mmHg to about 150 mmHg. Thereaction temperature may be increase to from about 200° C. to about 230°C. when the pressure reduced to from about 40 mmHg to about 80 mmHg, andthe reaction temperature may be increased to from about 220° C. to about275° C. when the pressure is reduced to about 20 mmHg to about 5 mmHg.

The reaction time may be any amount of time necessary to providesufficient polymerization and may vary with reactants, catalysts,reaction temperatures and pressures, and so on. The skilled artisan mayvary the reaction time according to such considerations. In general, thetotal reaction time may be from about 10 hours to about 40 hours, and insome embodiments, the total reaction time may be from about 15 hours toabout 25 hours. The reaction time for various steps or temperature andpressure intervals may also vary, and each step or interval mayindividually be from about 2 hours to about 20 hours. In certainembodiments, a lower temperature, higher pressure first step or intervalmay be from about 2 hours to about 6 hours in length, followed by alonger 10 hour to 25 hour step or interval where the temperature isincreased and the pressure is reduced. As discussed above, the reactiontime for each step or interval may vary and can be determined by theskilled artisan.

In some embodiments, the amine containing monomer may be provided in amolar excess to increase the number of amine end-groups on thephosphonamide oligmers. As discussed above the amine containing monomermay be any diamine, triamine, or polyamine known in the art. Inparticular embodiments, the amine containing monomer may be provided ina molar excess of at least 10%, and in other embodiments, the aminecontaining monomer may be provided in a molar excess of from about 10%to about 50%, about 10% to about 30%, or about 10% to about 25%. Withoutwishing to be bound by theory, when an amine containing monomer iscombined with a phosphodiester containing monomer and is provided in amolar excess of 10%, the resulting oligomeric phosphonamide may haveabout 5% excess amino end-groups versus phosphonate-ester end groups. Instill other embodiments, the reaction mixture may include a branchingagent, and the ratio of amine to phosphodiester containing monomers maybe adjusted to ensure excess amine end-groups in the resultingoligomeric phosphonamide.

In further embodiments, the amino terminated phosphonamides describedabove can be prepared by reacting diamines, triamines, polyamines, orcombinations thereof with phosphinic dihalides.

In various embodiments, amine containing monomer may be any knowndiamine, triamine, or polyamine containing monomer. Exemplary aminecontaining monomers include alkanediamines, alkanetriamines, arylamines,cycloalkylamines, or any combinations thereof, and in variousembodiments, the alkanediamines, alkanetriamines, arylamines,cycloalkylamines may have from about 6 to about 12 or about 20 carbonatoms. In particular embodiments, the alkanediamines, alkanetriamines,arylamines, cycloalkylamines may have from about 6 to about 8 carbonatoms. More specific non-limiting examples of suitable diamines,triamines, and polyamines include m-xylylenediamine,di(4-aminophenyl)methane, di(4-aminocyclohexyl)methane,2,2-di(4-aminophenyl)propane, 1,4-diaminobutane,1,3-bis-(aminomethyl)-cyclohexane, 1,4-bis(aminomethyl)-cyclohexane,2,5-bis(aminomethyl)-bicyclo-[2,2,1]heptane and/or2,6-bis-(aminomethyl)-bicyclo[2,2,1]heptane,bis-(4-aminocyclohexyl)-derivative of an alkane having from 1 to 6carbon atoms, and p-xylylene-diamine 2,2-di(4-aminocyclohexyl)propane,and triamine derivatives of these diamines, any mixtures, orcombinations thereof.

In particular embodiments, the amine containing monomer may be polyetheramines such as Jeffamines. Jeffamines are well known in the art and anypolyether amine or Jaffamine can be used to prepare the phosphonamideoligomers of the invention. In particular embodiments, the aminecontaining monomer may be a Jeffamine of the structures provided below.

Ave Name Structure x Mw D230 D2000

~2.5 ~33  230 2000 T403

n = 1 (x + y + z) = 5 − 6 R = CH₂CH₃  440

In certain embodiments, the phosphonate containing monomer may be adiaryl alkyl- or arylphosphonates or optionally substituted diarylalkyl- or arylphosphonates of embodiments may be of general formula (I):

where R₂ may be C₁-C₂₀ alkyl or, optionally substituted, aryl and R₁ maybe an aryl group, or a substituted aryl group of formula (II):

where R₃, R₄, R₅, R₆, and R₇ may independently be any substituentincluding but not limited to hydrogen, C₁-C₂₀ alkyl, aromatic or arylgroup, trifluoromethyl, nitro, cyano, halide (F, Cl, Br, I), C₁-C₂₀alkyl ether, C₁-C₂₀ alkyl ester, benzyl halide, benzyl ether, aromaticor aryl ether, or optionally substituted versions of these, and R₃, R₄,R₅, R₆, and R₇ are essentially unaffected by the reaction. In certainembodiments, the diaryl alkylphosphonate may be diphenylmethylphosphonate.

The amino terminated phosphonamides and oligomeric amino terminatedphosphonamides described above may include at least one amino termini,and in certain embodiments, the amino terminated phosphonamides andoligomeric amino terminated phosphonamides may have two or more aminotermini. In some embodiments, the molecular weight of the oligomericamino terminated phosphonamides may be substantially the same. In otherembodiments, the oligomeric amino terminated phosphonamides may bepresent in a statistical mixture of various molecular weight species. Insuch statistical mixtures, an amino group is present of both ends of thesame molecule, one end of the molecule, or on neither end of differentmolecules.

The oligomeric amino-terminated phosphonamides described herein overcomethe problems of toxicity and leaching while satisfying the UL orcomparable standardized flame resistance rating performance requirementswithout detracting from important physical, mechanical and processingproperties. This is achieved by formulating a composition of a reactivemonomer, oligomer or polymer and an effective amount of an aminoterminated phosphonamide oligomer. The amount of the amino terminatedphosphonamide may be provided in any appropriate flame retarding amountand can range up to about 50% by weight of the final composition, and insome embodiments, the amount of amino terminated phosphonamide may befrom about 10% to about 30%, by weight of the final composition. In someembodiments, the oligomeric amino-terminated phosphonamide can be curedwith the host resin, and in other embodiments, the oligomeric aminoterminated can be pre-reacted with the host resin.

The amino terminated phosphonamide oligomers of various embodiments canbe combined with a variety of other monomers, oligomers, and polymersincluding, for example, epoxies, ureas, esters, urethanes, and imides.In certain embodiments, the amino terminated phosphonamides andoligomeric amino terminated phosphonamide oligomers may be incorporatedinto thermoplastic and thermosetting polymers such as, but not limitedto, polyester, polycarbonate, polyacrylate, polyacrylonitrile,polystyrene (including high impact strength polystyrene and syndiotacticpolystyrene), polyurea, polyurethane, linear and branchedpolyphosphonates, poly(acrylonitrile butadiene styrene), polyimide,polyarylate, poly(arylene ether), polyethylene, polypropylene,polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride,bismaleimide polymer, polyanhydride, liquid crystalline polymer, epoxiesand polyepoxies, such as polymers resulting from the reaction of one ormore epoxy monomers or oligomers with one or more chain extenders orcuring agents such as a mono or multifunctional phenol, amine,benzoxazine, anhydride or combination thereof, benzoxazine,polyphosphate, cellulose polymer, or any combination thereof. Theseexemplary thermoplastics and thermosets are well known commerciallyavailable commodity engineering plastics that used in a variety ofapplications. Embodiments of the invention encompass any other suchengineering plastics not specifically included in the above lists, andcombinations of various thermoplastics and thermoset resins.

In some embodiments, the compositions including a thermoplastic orthermoset resin and an amino-terminated phosphonamide or an oligomericamino-terminated phosphonamide may further include other additives suchas, for example, one or more curing agents, additional flame retardantadditives, fillers, anti-dripping agents, and other additives typicallyused with such polymers. In some embodiments, the additional flameretardant additive may be a complementary flame retardant such as, butnot limited to, alumina trihydrate, magnesium hydroxide, organicsulfonate or sulfonamidate salts, siloxanes, (organic) phosphinatesalts, metal phosphinate salts, ammonium polyphosphate, melamine,melamine phosphate, melamine pyrophosphate, melamine polyphosphate,melamine cyanurate, red phosphorus, (poly)phosphonates, triphenylphosphate, or a bisphosphate flame retardant (such as resorcinolbis(diphenyl phosphate), or bisphenol A bis(diphenyl phosphate).

In certain embodiments, the amino terminated phosphonamide or oligomericamino-terminated phosphonamide may be formulated as fiber reinforcedcomposites. Such fiber reinforced composites may include any of thethermoplastics or thermosets described herein in combination with afiber or fabric that may be composed of carbon, glass, organic fiberssuch as polyester, polyaramide, inorganic fibers may include, but arenot limited to, silicon carbide. In some embodiments, the reinforcingfiber or fabric may be incorporated into the polymer matrix with theamino terminated phosphonamide or oligomeric amino-terminatedphosphonamide, and in other embodiments, the polymer resin, aminoterminated phosphonamide or oligomeric amino-terminated phosphonamidecan be used to impregnate a reinforcing fiber or fabric.

In particular embodiments, the oligomeric amino-terminated phosphonamidemay be provided in epoxy formulations. Such embodiments are not limitedto any particular type of epoxy. For example, the epoxy resin may be abisphenol A epoxy, bisphenol F epoxy, phenolic novolak epoxy, cresolnovolak epoxy, bisphenol A novolak epoxy resins, and the like. In someembodiments, the epoxy resins used in embodiments may be halogenated,and in other embodiments, the epoxy resins may be non-halogenated. Suchepoxy resins may be used in any application. The epoxies of suchembodiments including oligomeric amino-terminated phosphonamides may beincorporated into, for example, circuit boards, housing for electroniccomponents, epoxy encapsulant compositions for use in electronicapplications, and in other embodiments, epoxy compositions of theinvention can be used for structural applications and as coatings. Theoligomeric amino-terminated phosphonamides can be used in place ofbrominated flame retardants or other phosphorus containing flameretardants, or the oligomeric amino-terminated phosphonamides can beused in combination with such compositions. In some embodiments, epoxyresins compositions including oligomeric amino-terminated phosphonamidesmay contain other components conventionally used epoxies such as, butnot limited to, polyphenylene oxide, imide, phenolic, and benzoxazineresins as well as reinforcement additives such as paper, glass fibers,organic fibers, or carbon fibers.

In some embodiments, the oligomeric amino-terminated phosphonamide ofthe invention may be used in combination with polyurea. The oligomericamino-terminated phosphonamides can be incorporated into any polyureaformulation known in the art. For example, in certain embodiments, thepolyurea formulations may include diisocyanates, aromatic or aliphaticdiamines, or combinations thereof in addition to the amino terminatedphosphonamide.

In some embodiments, the oligomeric amino-terminated phosphonamide maybe used in crosslinked polymer compositions. In some embodiments, anoligomeric amino-terminated phosphonamides having two or more functionalamine groups per oligomer chain such as, but not limited to, thosedescribed in Formula I and Formula II can act as a crosslinking agent.These oligomeric amino-terminated phosphonamides can be combined with athermoplastic or thermoset resin having functional groups that can reactwith the amine groups of the oligomeric amino-terminated phosphonamide.For example, in particular exemplary embodiments, crosslinked polyureascan be produced by combining polyureas with the amino terminatedphosphonamides of embodiments of the invention, and, for example,triisocyanates, diisocyanates, aromatic or aliphatic diamines, orcombinations thereof.

In some embodiments, the oligomeric amino terminated phosphonamides canbe mixed or blended with other monomers, oligomers, or polymers andthese mixtures can be used for preparing articles of manufacture fromthe blended material. For example, some embodiments include methods forpreparing a polymer composition including the steps of blending in amelt a monomer, oligomer, or polymer and a oligomeric amino terminatedphosphonamide. The melt blending may be carried out by any mixingtechnique, for example, melt mixing may be carried out in a brabendermixer or extruder. In some embodiments, the methods may include thesteps of extruding the mixture after melt mixing and pelletizing theresulting material. In other embodiments, the methods may includecompressing the melt mixed material in rollers to create a film,spincasting a film, blowmolding a film or extruding a sheet product. Instill other embodiments, the methods may include molding the melt mixedmaterial into an article of manufacture. In still other embodiments theoligomeric amino terminated phosphonamide can be mixed in solution withother components and, optionally after mixing with another solution, besprayed to form a film.

Still other embodiments include polymeric compositions prepared fromthese amino terminated phosphonamide oligomers and other monomers,oligomers or polymers that meet UL fire or comparable standardized fireresistance ratings required for a variety of consumer products withoutdetracting from other important safety, environmental, manufacturing andconsumer use requirements. For example, consumer electronics must meetparticular fire resistance standards as specified by the Underwriter'sLaboratory (UL) or comparable standardized fire resistance ratingcriteria without compromising other properties such as Tg, HDT, andinterfacial adhesion. The electronics often contain circuit boards thatinclude epoxy/glass laminates. The state-of-the-art approach torendering these systems flame retardant is to use various additives suchas brominated compounds or compounds containing aluminum, antimony,and/or phosphorus. However, these compounds are often toxic, and canleach into the environment over time making their use less desirable. Insome countries these additives and related additive types are beingphased out of use.

Further embodiments include articles of manufacture that include apolymer matrix and the amino terminated phosphonamide or oligomericamino-terminated phosphonamide of the invention. For example, certainembodiments are directed to consumer electronics and other consumerproducts that must meet particular fire resistance standards asspecified by UL or other standardized criteria. Such consumerelectronics and consumer products may contain or include, for example,circuit boards, housings, or other components or subcomponents thatinclude amino terminated phosphonamide or oligomeric amino-terminatedphosphonamide containing compositions, filled amino terminatedphosphonamide or oligomeric amino-terminated phosphonamide containingcompositions, or fiber reinforced amino terminated phosphonamide oroligomeric amino-terminated phosphonamide compositions. The componentsfabricated from such compositions will generally meet the U1-94 V-0 orsimilar criteria for fire resistance while retaining good propertiessuch as Tg, HDT, interfacial adhesion, and the like.

EXAMPLES

Although the present invention has been described in considerable detailwith reference to certain preferred embodiments thereof, other versionsare possible. Therefore the spirit and scope of the appended claimsshould not be limited to the description and the preferred versionscontained within this specification. Various aspects of the presentinvention will be illustrated with reference to the followingnon-limiting examples.

Materials

Jeffamine diamines (D230, D2000 and T403) were purchased from HuntsmanPetrochemical Corporation. Expandable graphite—GRAFGUARD® 160-50 wasobtained from GrafTech International. Ammonium polyphosphonate (APP) (20μm powder) was obtained from ICL-LP. Diphenyl methyl phosphonate (DPP)was prepared using methods referred to in U.S. Pat. No. 7,888,534 B2 andU.S. Pat. No. 7,928,259 B2, Dragonshield-BC (DSBC™) was obtained fromSpecialty Products Inc. (SPI).

Example 1 Preparation of Oligomeric Amino Terminated Phosphonamides:

The reactions of various aromatic and aliphatic diamines withdiphenylmethyl phosphonate were carried out in a round bottom flaskfitted with a mechanical stirrer, N₂/vacuum inlet, and a distillationcolumn (filled with hollow glass tubes) wrapped with electrical heatingtape. The reagents were heated to 200° C. for 12-14 hrs., whilegradually lowering the vacuum from 400 mmHg to 5 mmHg. The temperaturewas then increased to 240° C. for 4-6 hrs at <1 mmHg (full vacuum) todrive off residual phenol and any unreacted starting materials. Theamino terminated phosphonamide product was isolated as a viscous liquid.The reaction was monitored by gas chromatography-mass spectroscopy(GC-MS) by analysis of the phenol by-product. The amino terminatedphosphonamide oligomer was analyzed using nuclear magnetic resonancespectroscopy (¹H-NMR) and the % phosphorus was determined usinginductively coupled plasma optical emission spectrometry (ICP-OES).

Example 2 Synthesis of an Amino Terminated Phosphonamide:

276.0 g (1.2 mol) Jeffamine D230, 297.8 g (1.2 mol) DPP and 3.05 g (0.03mol) magnesium chloride were added to a 1 L round bottom flask andheated to 200° C. while stirring for 14 hours. The vacuum was graduallylowered to 60 mmHg over 6 hrs., maintained at 40 mm Hg for 4 hrs, andthen lowered to 10 mmHg for 4 hrs. The distillation column wasmaintained at 115° C. for 14 hrs. The distillate was collected in aflask cooled in ice. After 14 hours, full vacuum was applied (<0.5 mmHg)and the temperature increased to 240° C. for 2.5 hrs. The product wasisolated as a highly viscous liquid (320.6 g). GC-MS analysis of thedistillate indicated the total phenol collected was 170.3 g (1.8 mol),residual diamine 23.2 g (0.1 mol) and residual DPP collected was 53.7 g(0.2 mol). Anal. % P=10.6 wt. %.

Example 3 Synthesis of an Amino Terminated Phosphonamide:

301.3 g (1.31 mol) Jeffamine D230, 259.3 g (1.05 mol) DPP and 3.05 g(0.03 mol) magnesium chloride were added to a 1 L round bottom flask andheated to 200° C. while stirring for 19 hours. The vacuum was graduallylowered to 60 mmHg over 9 hrs., and then lowered to 3.0 mmHg over 5 hrs.and held for 4 hrs. The distillation column was maintained at 115° C.The distillate was collected in a flask cooled in ice. After 19 hours,full vacuum was applied (<0.5 mm Hg) and the temperature increased to230° C. for 1 hr. The product was isolated as a highly viscous liquid(276.3 g). GC-MS analysis of the distillate indicated the total phenolcollected was 178.3 g (1.9 mol), residual diamine 66.7 g (0.3 mol) andresidual DPP collected was 24.5 g (0.1 mol). Molecular weight (Mw 670,Mn 570) (GPC, PS standards). Anal. % P=10.4 wt. %.

Example 4 Synthesis of an Amino Terminated Phosphonamide:

956.2 g (0.48 mol) Jeffamine D2000, 109.2 (0.44 mol) DPP and 2.67 g(0.028 mol) magnesium chloride were added to a 3 L round bottom flaskand heated to 200° C. while stirring for 18.5 hours. The vacuum wasgradually lowered to 20 mmHg over 3 hrs. and held for 11.5 hrs., andthen to 5 mm Hg for 4 hrs. The distillation column was maintained at115° C. for 6.5 hrs. and then increased to 140° C. The distillate wascollected in a flask cooled in ice. After 18.5 hrs., full vacuum wasapplied (<0.5 mm Hg) for 4.5 hrs. at 200° C. Then, the temperatureincreased to 215° C. for 1.0 hr., and to 240° C. for 2.5 hrs. Theproduct was isolated as a highly viscous liquid (969 g). GC-MS analysisof the distillate indicated the total phenol collected was 66.2 g (0.7mol), and residual DPP collected was 13.6 g (0.05 mol). Anal. % P=1.3wt. %.

Example 5 Synthesis of an Amino Terminated Phosphonamide:

175.0 g (0.39 mol) Jeffamine T403, 124.1 g (0.5 mol) DPP and 1.24 g(0.013 mol) magnesium chloride were added to a 500 mL round bottom flaskand heated to 200° C. while stirring for 7 hours. The vacuum wasgradually lowered to 55 mmHg over 2 hrs, then to 5 mm Hg over 5 hrs. Thedistillation column was maintained at 115° C. The distillate wascollected in a flask cooled in ice. After 7 hrs., full vacuum wasapplied (0.1 mm Hg) for 2 hrs at 200° C., and then increased to 250° C.for 2 hrs. After 2 hrs. the product cross-linked in the flask and thereaction was discontinued. The product was removed from the flask bybreaking the flask and 48.1 g of solid was recoverable. Total phenolcollected was 73.0 g (0.8 mol), and residual unreacted triamine 9.6 g(0.02 mol) and 17.6 g DPP (0.07 mol). Anal. % P=6.5 wt %

Example 6 Synthesis of an Amino Terminated Phosphonamide:

175.0 g (0.39 mol) Jeffamine T403, 124.1 g (0.5 mol) DPP and 1.24 g(0.013 mol) magnesium chloride were added to a 500 mL round bottom flaskand heated to 200° C. while stirring for 14 hours. The vacuum wasgradually lowered to 25 mmHg over 3 hrs., then to 5 mm Hg for 11 hrs.The distillation column was maintained at 115° C. The distillate wascollected in a flask cooled in ice. After 14 hrs., full vacuum wasapplied (<0.5 mm Hg) for 4.5 hrs. at 200° C. The product was isolated asa solid (219.1 g). GC-MS analysis of the distillate indicated the totalphenol collected was 72.3 g (0.8 mol), and no residual triamine or DPPwas collected. Anal. % P=7.3 wt. %.

Example 7 Synthesis of an Amino Terminated Phosphonamide:

1789 g (0.90 mol) Jeffamine D2000, 203 g (0.82 mol) DPP and 0.5 g (0.005mol) magnesium chloride were added to a 3 L round bottom flask andheated to 200° C. while stirring under vacuum (250 mmHg). After 4.5 hrs,the vacuum was gradually lowered to 10 mmHg over 8 hrs. and then to 5 mmHg for 4 hrs. After 16.5 hrs., full vacuum was applied (<0.5 mm Hg), andthe temperature increased to 225° C. for 1.0 hr. and then to 240° C. for3.5 hrs. The distillation column was maintained at 115° C. for 16.5 hrs.and then increased to 140° C. The distillate was collected in a flaskcooled in ice. The product was isolated as a highly viscous liquid (1855g). GC-MS analysis of the distillate indicated the total phenolcollected was 123.6 (1.31 mol), and residual DPP collected was 0.4 g(0.002 mol). Anal. % P=1.3 wt. %.

Example 8 Synthesis of an Amino Terminated Phosphonamide:

1789 g (0.90 mol) Jeffamine D2000, 203 g (0.82 mol) DPP and 0.5 g (0.005mol) magnesium chloride were added to a 3 L round bottom flask andheated to 200° C. while stirring under vacuum (250 mmHg). After 4.5hrs., the vacuum was gradually lowered to 10 mmHg over 8 hrs and then to5 mm Hg for 4 hrs. After 16.5 hrs., full vacuum was applied (<0.5 mmHg), and the temperature increased to 225° C. for 1.0 hr., and then to240° C. for 3.5 hrs. The distillation column was maintained at 115° C.for 16.5 hrs. and then increased to 140° C. The distillate was collectedin a flask cooled in ice. The product was isolated as a highly viscousliquid (1843 g). GC-MS analysis of the distillate indicated the totalphenol collected was 90.2 g (0.96 mol), and residual DPP collected was19.0 g (0.08 mol). Anal. % P=1.3 wt. %.

Example 9 Amino Terminated Phosphonamide Oligomers in Polyureas:

Polyurea formulations are generally prepared by the reaction of diamineswith diisocyanates. In order to produce flame retardant polyureas,several phosphorus based diamines (FRX diamines) were prepared and addedto the diamine formulations used to prepare blast mitigation coatings.(Scheme 1).

Example 10

Polyurea Films with Amine Terminated Phosphonamide Oligomers:

Polyurea films were prepared by spraying out a combination ofdiisocyanates (A-side) and diamines (B-side) onto primed concrete boardsof 6 inches×18 inches for flammability testing. The thickness of eachcoating was 90 mils (0.09 inches). The test was conducted in accordancewith the ASTM E-162, “Standard Method of Test for Surface Flammabilityof Materials Using a Radiant Heat Energy Source.” The spray-coatedboards are mounted in a frame placed facing the radiant panel, butinclined at an angle of 30 degrees from top downward. A pilot burneradjusted to provide a 6″ to 7″ flame serves to ignite the sample at thetop. The material under test burns downward.

Oligomeric amine terminated phosphonamides were added to the B-side ofthe mixture during formulation. Phosphorus-based additives—diphenylmethylphosphate (DPP) and ammonium polyphosphate (APP)—were also testedas additives in the A-side and the B-side, respectively. Graphite wasadded to various formulations to prevent dripping during burning. Thebase formulation was Dragonshield BC™ (DSBC™).

DSBC™ Formulations containing the commercial flame retardant additiveammonium polyphosphonate (APP) were prepared and evaluated in comparisonto phosphonamide oligomers. Due to processability during formulation,the optimal loading of the amine-terminated phosphonamide oligomerPA-D2000 was 17 wt. %.

Tables 1-2 provide results from ASTM E162 testing of the FR polyureasamples. The results are recorded as a Flamespread Index determined fromprogression time of the flame at 3, 6, 9, 12, and 15 inch interval marksmeasured from the top of the sample. The maximum temperature increaseresulting from the burning sample was measured by 8 thermocouplesconnected in parallel and located in the sheet metal stack above thetested sample. The Flamespread Index (FSI) is derived by the followingformula:

Is=Fs×Q

where Is is the Flamespread Index, Fs is the Flamespread Factor, and Qis the Heat Evolution Factor. The flamespread classification system usedby most of the model building codes and the National Fire ProtectionAssociation Life Safety Code, NFPA No. 101, encompasses the following:

Class A (I)—0 to 25 Flamespread Index

Class B (II)—26 to 75 Flamespread Index

Class C (III)—76 to 100 Flamespread Index

The results of FSI testing of various polyurea compositions includingoligomeric amino-terminated phosphonamides are provided in Table 1.

TABLE 1 Polyurea FR Testing: Flame Spread Index (FSI) Results Wt %Additives in DSBC ™ Formulation B-Side A-Side PA-D2000 Total ASTM FSI #DPP Graphite (Example 3) APP % P E162 Class 1 0 0 0 0 0 212 Fail 2 0 2 010 1.0 114 Fail 3 0 5 0 10 1.0 64 B 4 0 5 0 20 2.6 54 B 5 0 5 17 0 0.189 C 6 8 5 0 10 1.5 70 B 7 8 5 17 0 0.6 47 B

TABLE 2 Polyurea FR Testing: Flame Spread Index (FSI) Results Wt %Additives in DSBC ™ Formulation B-Side A-Side PA-D2000 Total ASTM FSI #DPP Graphite (Example 6) APP % P E162 Class 1 0 0 0 0 0 212 Fail 2 0 100 2 0.3 34 B 3 8 10 17 2 0.9 13 A

Example 11 Evaluation of FR Behavior of Phosphonamides in Bisphenol-AEpoxies

The FR performance of cured epoxy resin samples with and withoutphosphonamides was evaluated, and the results are provided in Table 3.The samples were prepared by mixing the amine-terminated phosphonamideoligomers with the epoxy resin and curing in an oven at 60° C. for 48hr. The FR was evaluated by holding a flame to the sample for 10 secondsand observing for self-extinguishing behavior. The formulationcontaining the amine terminated phosphonamide oligomer (PA-D230 Example2) exhibited self-extinguishing behavior, whereas the formulationcontaining the diamine (D230) continued to burn.

TABLE 3 Epoxy formulations with phosphonamides Amine-terminated PA-D230compound D230 (Example 2) Weight (g) 6.5 6.5 Epoxy resin (g) 5 5 Diethyltriamine (g) 0 0.5 Total % P 0 5.6 FR evaluation- no yesSelf-extinguishing

1. A composition comprising amino terminated phosphonamides of generalFormula I:

wherein: R is a C₁ to C₂₀ alkyl or substituted aryl group; Z is:

 and each —NH—X—NH— is derived from an alkanediamine, alkanetriamine,arylamine, or cycloalkylamine having from about 6 to about 20 carbonatoms; and n is an integer of from 1 to about 20, wherein at least oneamino terminated phosphonamide Z is

 and the amino-terminated phosphonamide comprises at least about 50%amine end-groups based on the total number of end groups.
 2. Thecomposition of claim 1, wherein n is an integer of from 1 to about 10.3. (canceled)
 4. The composition of claim 1, wherein R is methyl.
 5. Thecomposition of claim 1, wherein each —NH—X—NH— is derived from adiamine, a triamine, or a polyamine. 6-7. (canceled)
 8. The compositionof claim 1, further comprising one or more monomer, oligomer, orpolymer.
 9. The composition of claim 1, further comprising one or morepolycarbonates, epoxy derived polymers, polyepoxies, benzoxazines,polyacrylates, polyacrylonitriles, polyesters, poly(ethyleneterephthalate)s, poly(trimethylene terephthalate) and poly(butyleneterephthalate)s, polystyrenes, polyureas, polyurethanes,polyphosphonates, poly(acrylonitrile butadiene styrene)s, polyimides,polyarylates, poly(arylene ether)s, polyethylenes, polypropylenes,polyphenylene sulfides, poly(vinyl ester)s, polyvinyl chlorides,bismaleimide polymers, polyanhydrides, liquid crystalline polymers,cellulose polymers, and combinations thereof.
 10. The composition ofclaim 1, further comprising one or more fillers, fibers, surfactants,organic binders, polymeric binders, crosslinking agents, couplingagents, additional flame retardants, anti-dripping agents, anti-staticagents, catalysts, colorants, inks, dyes, antioxidants, stabilizers, orcombinations thereof. 11-20. (canceled)
 21. A resin compositioncomprising: units derived from amino terminated phosphonamides ofgeneral Formula I:

wherein: R is a C₁ to C₂₀ alkyl or substituted aryl group; Z is:

and each —NH—X—NH— is derived from an alkanediamine, alkanetriamine,arylamine, or cycloalkylamine having from about 6 to about 20 carbonatoms; n is an integer of from 1 to about 20; and wherein at least oneamino terminated phosphonamide Z is

and the amino-terminated phosphonamide comprises at least about 50%amine end-groups based on the total number of end groups; and one ormore monomer, oligomer, or polymer covalently associated with the unitsderived from the amino terminated phosphonamide.
 22. The resincomposition of claim 21, wherein the one or more monomer, oligomer, orpolymer comprises units derived from a phosphonate, isocyanate, epoxy,carboxylic acid, carboxylic acid ester, or combinations thereof.
 23. Theresin composition of claim 21, wherein the one or more monomer,oligomer, or polymer comprises one or more polycarbonates, epoxy derivedpolymers, polyepoxies, benzoxazines, polyacrylates, polyacrylonitriles,polyesters, poly(ethylene terephthalate)s, poly(trimethyleneterephthalate) and poly(butylene terephthalate)s, polystyrenes,polyureas, polyurethanes, polyphosphonates, poly(acrylonitrile butadienestyrene)s, polyimides, polyarylates, poly(arylene ether)s,polyethylenes, polypropylenes, polyphenylene sulfides, poly(vinylester)s, polyvinyl chlorides, bismaleimide polymers, polyanhydrides,liquid crystalline polymers, cellulose polymers, and combinationsthereof.
 24. The resin composition of claim 21, further comprising atleast one other polymer or oligomer to make a blend or mixture.
 25. Theresin composition of claim 21, further comprising one or more fillers,fibers, surfactants, organic binders, polymeric binders, crosslinkingagents, coupling agents, additional flame retardants, anti-drippingagents, anti-static agents, catalysts, colorants, inks, dyes,antioxidants, stabilizers, or combinations thereof.
 26. An article ofmanufacture comprising amino terminated phosphonamide oligomers ofFormula I:

wherein: R is a C₁ to C₂₀ alkyl or substituted aryl group; Z is:

 and each —NH—X—NH— is derived from an alkanediamine, alkanetriamine,arylamine, or cycloalkylamine having from about 6 to about 20 carbonatoms, wherein at least one amino terminated phosphonamide Z is

 and the amino-terminated phosphonamide comprises at least about 50%amine end-groups based on the total number of end groups.
 27. Thearticle of manufacture of claim 26, wherein the article of manufacturecomprises a coating, adhesive, prepreg, foam, film, extruded sheet,fiber, molding, fiber reinforced laminate, fiber reinforced circuitboard, or combination thereof.
 28. The article of manufacture of claim26, wherein the article of manufacture comprises a consumer product. 29.The article of manufacture of claim 26, wherein the article ofmanufacture exhibits a limiting oxygen index (LOI) of at least
 27. 30.The article of manufacture of claim 26, wherein article exhibits anUnderwriters Laboratory-94 (UL-94) of V-0 measured at a thickness of 0.8mm. 31-39. (canceled)